Hci salts of the condensation product of an epihalohydrin with an aliphatic primary or secondary amine



United States Patent O HCl SALTS OF THE CONDENSATION PRODUCT OF AN EPIHALOHYDRIN WITH AN ALHHATIC PRIMARY R SECONDARY AIVHNE Ernest L. Pollitzer, Hinsdale, Ill., assignor to Universal Oil Products Company, Des Plaines, 111., a corporation of Delaware No Drawing. Filed June 22, 1961, Ser. No. 118,760

8 Claims. (Cl. 260404.5)

This is a continuation-in-part of co-pending application Serial No. 753,894, filed August 8, 1958, now Patent No. 3,017,358, January 16, 1962, and relates to a novel composition of matter.

The novel composition of matter of the present invention is particularly useful in preventing heat exchanger deposits. In most refining operations economies are effected by utilizing the heat contained in hot products of the process to partially or completely heat the charge to the process or other low temperature streams. At the same time this serves to cool the hot products prior to further separation or treatment. This transfer of heat normally is accomplished by passing the hot products in indirect heat exchange with the cooler products. However, difficulty is experienced in the efiicient transfer of heat due to the formation of deposits in the heat exchanger, which deposits interfere with the satisfactory transfer of heat and, in extreme cases, results in plugging of the heat exchanger. This in turn means that the unit must be completely shut down in order to clean or replace the heat exchanger. It is apparent that this is a serious problem and incurs great expense in shutting down the unit, both in the cost of cleaning or replacing the heat exchanger, as well as in the loss of products to be marketed. The present invention is directed to a novel method of preventing such heat exchanger deposits.

More particularly the present invention is directed to a modification of certain additives as will be set forth in detail hereinafter. These additives are effective for use in hydrocarbon oils to improve storage properties thereof, preventing sediment and sludge formation, discoloration and other undesirable deterioration of the hydrocarbon oil. However, hydrocarbon oils from different sources respond differently to different additives. Accordingly, the additives referred to above are effective for various purposes in some oils but are satisfactory for only limited purposes in other oils. For example, some of these additives satisfactorily stabilize the oil against deterioration in storage but will not satisfactorily prevent deposit formation in heat exchangers. As hereinbefore set forth, the novel additive of the present invention is particularly effective in preventing heat exchanger deposits and, at the same time, will serve to improve the storage stability of hydrocarbon oils.

In one embodiment the present invention relates to an oil soluble HCl salt of a compound selected from the group consisting of (1) the condensation product of an epihalohydrin compound with an amine compound, (2) carboxylic acid ester thereof, (3) partial phosphate salt of said condensation product, and (4) partial phosphate salt of said carboxylic acid ester.

In a specific embodiment the present invention relates to an oil soluble HCl salt of the condensation product of epichlorohydrin with tallow amine, said salt having from about 1% to about 20% of the amino nitrogen neutralized with HCl.

As hereinbefore set forth, the novel additive of the present invention is an HCl salt of the condensation product of an epihalohydrin compound with an amine compound or derivatives thereof. The condensation product and the derivatives thereof will be described under subheadings to facilitate the explanation of the invention.

3,217,018 Patented Nov. 9, 1965 CONDENSATION PRODUCT OF EPIHALOHYDRIN WITH AMINE Any suitable epihalohydrin compound may be utilized in preparing the condensation product thereof with an amine. Epichlorohydrin is preferred. Other epichlorohydrin compounds include 1,2-epi-4-chlorobutane, 2,3- epi-4-chlorobutane, 1,2-epi-5-chloropentane, 2,3-epi-5 chloropentane, etc. In general, the chloro derivatives are preferred, although it is understood that the corresponding bromo and iodo compounds may be employed. In some cases epidihalohydrin compounds may be utilized. It is understood that the different epihalohydrin compounds are not necessarily equivalent and that, as hereinbefore set forth, epichlorohydrin is preferred.

Any suitable alkyl amine may be used in preparing the condensation product. It is essential that the alkyl amine is a primary or secondary amine; that is, only one or two of the hydrogen atoms attached to the nitrogen atoms are substituted by alkyl groups, and reference to amine and amine compound in the present specifications and claims is intended to be limited accordingly. The preferred amine compound is a primary alkyl amine which, in a specifically preferred embodiment, contains from about 12 to about 40 carbon atoms per molecule. Illustrative primary alkyl amines include dodecyl amine, tridecyl amine, tetradecyl amine, pentadecyl amine, hexadecyl amine, heptadecyl amine, octadecyl amine, nonadecyl amine, eicosyl amine, heneicosyl amine, docosyl amine, tricosyl amine, tetracosyl amine, pentacosyl amine, hexacosyl amine, heptacosyl amine, octacosyl amine, nonacosyl amine, triacontyl amine, hentriacontyl amine, dotriacontyl amine, tritriacontyl amine, tetratriacontyl amine, pentatriacontyl amine, hexatriacontyl amine, heptatriacontyl amine, octatriacontyl amine, nonatriacontyl amine, tetracontyl amine, etc. Conveniently the long chain amines are prepared from fatty acids or more particularly from mixtures of fatty acids formed as products or lay-products. Such mixtures are available commercially, generally at lower prices and, as another advantage of the present invention, the mixtures may be used without the necessity of separating individual amines in pure state.

An example of such a mixture is hydrogenated talloW amine which is available under various trade names including Alamine H26D and Armeen HTD. These products comprise mixtures predominating in alkyl amines containing 16 to 18 carbon atoms per alkyl group, although they contain a small amount of alkyl groups having 14 carbon atoms, and also meet the other requirements hereinbefore set forth.

Illustrative examples of secondary amines include di- (dodecyl) amine, di-(tridecyl) amine, di-(tetradecyl) amine, di-(pentadecyl) amine, di-(hexadecyl) amine, di- (heptadecyl) amine, di-(octadecyl) amine, di-(nonadecyl) amine, di-(eicosyl) amine, etc. In another embodiment, which is not necessarily equivalent, the secondary amine will contain one alkyl group having at least 12 carbon atoms and another alkyl group having less than 12 carbon atoms. In most cases both of the alkyl groups have a straight chain of at least 3 carbon atoms attached to the nitrogen atom. Illustrative examples of such compounds include N-propyldodecyl amine, N-butyl-dodecyl amine, N-amyl-dodecyl amine, N-butyl-tridecyl amine, N-amyl-tridecyl amine, etc. Here again, mixtures of secondary amines are available commercially, usually at a lower price, and such mixtures may be used in accordance with the present invention. An example of such a mixture available commercially is Armeen 2HT which consists primarily of dioctadecyl amine and dihexadecyl amine.

Preferred examples of N-alkyl polyamines comprise N-alkyl-1,3-diaminopropanes and still more preferably such compounds in which the alkyl group contains at least 12 carbon atoms. Illustrative examples include N- dodecyl-1,3-diaminopropane, N-tridecyl-l,B-diaminopropane, N-tetradecyl-1,3-diaminopropane, N-pentadecyl- 1,3 diaminopropane, N hexadecyl 1,3 diaminopro- .pane, N heptadecyl 1,3 diaminopropane, N octadecyl 1,3 diaminopropane, N nonadecyl 1,3 diaminopropane, N-eicosyl-l,3-diaminopropane, N-heneicosyl-1,3-diaminopropane, N docosyl 1,3-diaminopropane, N-tricosyl-1,3-diaminopropane, N-t-etracos'yl-1,3- diaminopropane, Npentacosy1-1,3-diaminopropane, etc. As before, mixtures are available commercially, usually at lower prices, of suitable compounds in this class and advantageously are used for the purposes of the present invention. One such mixture is Duomeen T which is N-tallow-1,3-diaminopropane and predominates in alkyl groups containing 16 to 18 carbon atoms each, although the mixture contains a small amount of alkyl groups containing 14 carbon atoms each. Another mixture available commercially is N-coco-1,3-diaminopropane which contains alkyl groups predominating in 12 to 14 carbon atoms each. Still another example is N-soya-1,3-diaminopropane which predominates in alkyl groups containing 18 carbon atoms per group, although it contains a small amount of alkyl groups having 16 carbon atoms.

While the N-alkyl-1,3-diaminopropanes are preferred compounds of this class, it is understood that suitable N-alkyl ethylene diamines, N-alkyl-l,3-diaminobutanes, N-alkyl-l,4-diaminobutanes, N alkyl 1,3-diaminopentanes, N-alkyl-l,4-diaminopentanes, N-alkyl-1,5-diaminopentanes, N-alkyl-l,3-diaminohexanes, N-alkyl-1,4-diaminohexanes, N-alkyl-l,S-diaminohexanes, N-alkyl-1,6- diaminohexanes, etc. may be employed but not necessarily with equivalent results. Also, it is understood that polyamines containing 3 :or more nitrogen atoms may be employed in some cases. In other cases, polyamino alkanes may be employed as, for example, 1,12- diaminodecane, 1,13-diaminotridecane, etc.

In general the preferred amine compounds are saturated; i.e., do not contain double bonds in the chain. However, in some cases, unsaturated compounds may be employed, although not necessarily with equivalent results. Such amine compounds may be prepared from unsaturated fatty acids and, therefore, may be available commercially at lower cost. Illustrative examples of such amine compounds include dodecylenic amine, didodecylenic amine, N-dodecylenic ethylene diamine, .N-dodecylenic-1,3-diaminopropane, oleic amine, dioleic \amine, N-oleic ethylene diamine, N-oleic-1,3-diaminopropane, linoleic amine, dilinoleic amine, N-linoleic ethylene diamine, N-linoleic-1,3-diaminopropane, etc. It is understood that these amine compounds are included in the present specifications and claims by reference to amine or amine compounds.

In another embodiment of the invention, two different amines may be reacted with the epihalohydrin compound. Both of the amines may be selected from those hereinbefore set forth or one of the amines is selected from those hereinbefore set forth and the other amine is selected from ethylene diamine, diethylene triamine, triethylcne tetramine, tetraethylene penta'mine, etc., similar propylene and polypropylene polyamines, butylene and polybutylene polyamines, etc.

In general, 1 or 2 mols of amine compound are reacted with 1 or 2 mols of epihalohydrin compound. It is understood that, in some cases, an excess of amine or of epihalohydrin may be supplied to the reaction zone in order to insure complete reaction, the excess being removed subsequently in any suitable manner. When 2 mols of amine are reacted per mol of epihalohydrin compound, the amine may comprise the same or different amine compound.

In a preferred embodiment, the reaction of 1 mol of amine compound with lmol of epihalohydrin compound proceeds to the formation of polymeric reaction product. In this embodiment, the reaction is first effected at a temperature within the range hereinafter set forth, with only a portion of the reactants being present in the reaction mixture. After the initial reaction is completed, the remaining reactants are supplied to the reaction mixture and the reaction is completed at a higher temperature but within the same range set forth herein. For example, a portion of the amine may be first reacted with the epihalohydrin and then the remaining portion of the amine is reacted. These polymers may contain from about 3 to about 20 or more recurring units and preferably from about 5 to about 10 recurring units.

The desired quantity of alkyl amine and epihalohydrin compounds may be supplied to the reaction zone and therein reacted, although generally it is preferred to supply one reactant to the reaction zone and then introduce the other reactant step-wise. Thus, usually it is preferred to supply the amine to the reaction zone and to add the epihalohydrin compound step-wise, with stirring. When it is desired to react two different alkyl amines with the epihalohydrin compound, the epihalohydrin compound is supplied to the reaction zone. One of the amines is added gradually, and the reaction completed, followed by the addition of the second alkyl amine. Generally, it is preferred to utilize a solvent and, in the preferred embodiment, a solution of the amine in a solvent and a separate solution of the epihalohydrin compound in a solvent are prepared, and these solutions then are commingled in the manner hereinbefore set forth. Any suitable solvent may be employed, a particularly suitable solvent comprising an alcohol including ethanol, propanol, butanol, etc., 2-propanol being particularly desirable.

The reaction is effected at any suitable temperature, which generally will be within the range of from about 20 to about C. and preferably is within the range of from about 50 to about 75 C. A higher temperature range of from about 30 to about C. or more, and preferably of from about 50 to about 100 C., is specified when the reaction is effected at superatmospheric pressure to increase the reaction velocity. Conveniently, this reaction is effected by heating the amine solution at refluxing conditions, with stirring, gradually adding the epihalohydrin compound thereto, and continuing the heating until the reaction is completed.

Either before or after removal of the reaction product from the reaction zone, the product is treated to remove halogen, generally in the form of an inorganic halide as, for example, the sodium halide. This may be effected in any suitable manner and generally is accomplished by reacting the product with a strong inorganic base such as sodium hydroxide, potassium hydroxide, etc., to form the corresponding metal halide. The reaction to form the metal halide generally is effected under the same conditions as hereinbefore set forth. After this reaction is completed, the metal halide is removed in any suitable manner, including filtration, centrifugal separation, etc. It is understood that the reaction product also is heated sufficiently to remove alcohol and water and this may be effected either before or after the treatment to remove the inorganic halide.

In still another embodiment, after the reaction product of an alkyl amine and epihalohydrin is prepared, the reaction product may be reacted with other nitrogencontaining compounds including, for example, alkanol amines, urea, etc., instead of with the same or different alkyl amine as hereinbefore described. Illustrative alkanol amines include ethanol amine, propanol amine, butanol amine, pentanol amine, hexanol amine, etc.

ESTER OF THE CONDENSATION PRODUCT As hereinbefore set forth, another embodiment of the present invention comprises an HC-l salt of an ester of the condensation product of epihalohydrin compound and amine compound. Any suitable carboxylic acid may be used in forming the ester and in one embodiment preferably comprises a monobasic carboxylic acid containing at least 6 carbon atoms, more particularly from 6 to about 25 carbon atoms, and thus includes caproic, caprylic, lauric, myristic, palmitic, stearic, arachidic, behenic, lignoceric, cerotic, etc., decylenic, dodecylenic, palmitoleic, oleic, ricinoleic, petroselinic, vaccenic, linoleic, linolenic, eleostearic, licanic, parinaric, gadoleic, arachidonic, cetoleic, erucic, selacholeic, etc. However, in some cases, lower monobasic carboxylic acids may be employed and thus include formic, acetic, propionic, butyric, valeric, trimethylacetic, etc.

In another embodiment a polycarboxylic acid is used in forming the ester and preferably comprises a dibasic carboxylic acid containing at least 6 and preferably at least 10 carbon atoms per molecule, and more particularly from about to about 50 carbon atoms per molecule. The preferred acids are referred to herein as high molecular weight polybasic carboxylic acids and include adipic, pimelic, suberic, azelaic, sebacic, phthalic, etc., aconitic, citric, etc., hemimellitic, trimesic, prehnitic, mellophanic, pyromellitic, mellitic, etc., and higher molecular polybasic carboxylic acids. It is understood that a mixture of acids may be employed.

A particularly preferred acid comprises a mixed byproduct acid being marketed commercially under the trade name of VR-l Acid. This acid is a mixture of polybasic acids, predominantly dibasic, has an average molecular weight by basic titration of about 750, is a liquid at 77 F., has an acid number of about 150 and iodine of about 36, and contains about 37 carbon atoms per molecule.

Another particularly preferred acid comprises a mixed acid being marketed commercially under the trade name of Empol 1022. This dimer acid is a dilinoleic acid and is represented by the following general formula:

This acid is a viscous liquid, having an apparent molecular weight of approximaely 600. It has an acid value of 180-192, an iodine value of 8095, a saponification value of 185195, a neutralization equivalent of 290310, a refractive index at C. of 1.4919, a specific gravity at 15.5 C./l5.5 C. of 0.95, a flash point of 530 F., a fire point of 600 F., and a viscosity at 100 C. of 100 centistokes.

As hereinbefore set forth, dibasic acids containing at least 6 carbon atoms per molecule are preferred. However, it is understood that dibasic acids containing less than 6 carbon atoms also may be employed in some cases and thus include oxalic, malonic, maleic, succinic, glutaric, etc.

In another embodiment, the carboxylic acid used in forming the ester is a reaction product of a terpene and an alpha,beta-unsaturated carboxylic acid or anhydride. Any suitable terpenic compound may be reacted with any suitable alpha,beta-unsaturated polycarboxylic acid or anhydride to form the reaction product for subsequent condensation with the epichlorohydrin-amine condensation product. In one embodiment a terpene hydrocarbon having the formula C H is employed, including alphapinene, beta-pinene, dipentane, d-limonene, l-limonene and terpinoline. These terpene hydrocarbons have boiling points ranging from about 150 to about 185 C. In another embodiment the terpene may contain three double bonds in monomeric form, including terpene such as alloo-cymene, o-cymene, myrcene, etc. Other terpenic compounds include alpha-terpinene, p-cymene, etc.

As hereinbefore set forth, the terpene is reacted with an alpha,beta-unsaturated polycarboxylic acid or anhydride thereof. Any unsaturated polycarboxylic acid having a point of unsaturation between the alpha and beta carbon atoms may be employed. Illustrative unsaturated dicarboxylic acids include maleic acid, fumaric acid, citraconic acid, mesaconic acid, aconitic acid, itaconic acid, etc. While the dicarboxylic acids are preferred, it is understood that alpha,beta-unsaturated polycarboxylic acids containing three, four or more carboxylic acid groups may be employed. Furthermore, it is understood that a mixture of alpha,beta-unsaturated polycarboxylic acids and particularly of alpha,beta-unsaturated dicarboxylic acids may be used.

While the alpha,beta-unsaturated polycarboxylic acid may be employed, advantages appear to be obtained in some cases when using the anhydrides thereof. Illustrative anhydrides include maleic anhydride, citraconic anhydride, aconitic anhydride, itaconic anhydride, etc. It is understood that a mixture of anhydrides may be employed and also that the anhydride may contain substituents and particularly hydrocarbon groups attached thereto.

The reaction of terpene and alpha,beta-unsaturated acid or anhydride generally is effected at a temperature of from about to about 300 C., and preferably of from about to about 200 C. The time of heating will depend upon the particular reactants and may range from 2 hours to 24 hours or more. When desired, a suitable solvent may be utilized. Following the reaction, impurities or unreacted materials may be removed by vacuum distillation or otherwise, to leave a resinous product which may be a viscous liquid or a solid.

A terpene-maleic anhydride reaction product is available commercially under the trade name of Petrex Acid. This acid is a stringy, yellow-amber colored mass and is mostly di-basic. It has an acid number of approximately 530, a molecular weight of approximately 215 and a softening point of 40-50 C.

In preparing the ester of the condensation product of epihalohydrin compound and amine compound, the aliphatic carboxylic acids generally are preferred as hereinbefore set forth. However, in some cases, cyclic carboxylic acids may be employed. Aromatic carboxylic acids include benzoic acid, toluic acid, etc., which acids also may contain hydrocarbon and particularly alkyl substituents attached to the ring. Naphthenic carboxylic acids include cyclopentane carboxylic acid; cyclopentylacetic acid, methylcyclopentyl acid, camphonanic acid, cyclohexane carboxylic acid, methylcyclohexane carboxylic acid, dimethylcyclohexane carboxylic acid, trimethylcyclohexane carboxylic acid, etc.

It is understood that the various acids which may be used in preparing the ester are not necessarily equivalent and also that mixtures of acids may be employed in preparing the esters. In some cases, in place of the acid, the anhydride or certain esters of the acid may be utilized in forming the ester with the condensation product of epihalohydrin-amine. These esters may contain up to about 8 carbon atoms in the alcohol portion of the ester but preferably contain 1 or 2 carbon atoms. The alcohol portion must be volatile under the conditions of the esterification of the epihalohydrin-amine condensation product. In the esterification of the condensation product, transesterification occurs; that is, the smaller alcohol group is volatilized off and replaced by the epihalohydrin-amine condensation product.

The ester of the carboxylic acid and epihalohydrinamine condensation product may comprise the partially or completely esterified product. As hereinbefore set forth, the epihalohydrin-amine condensation product may and preferably contains a number of recurring units, each of the recurring units having a hydroxyl group. Accordingly, it Will be seen that one, all or any number of the hydroxyl groups may be esterified with the acid. Generally it is preferred to use stoichiometric amounts of these reactants in order to effect substantially complete esterification. One mol equivalent of carboxylic acid 7 4 will be used per each equivalent of hydroxyl group in the: epihalohydrin-amine condensation product.

The ester may be prepared in any suitable manner and, in general, is prepared readily by refluxing the acid and condensation product, preferably with the continuous removal of water formed in the reaction. The refluxing is continued until the theoretical amount of water is collected and thus may range from 1 hour to 48 hours or more at: a temperature above about 80 C. Although the esterification may be effected in the absence of a solvent, which generally will require the use of vacuum, normally it is; preferred to utilize a solvent. The exact temperature of refluxing will depend upon the particular solvent employed. For example, with benzene as the solvent, the temperature will be in the order of 80 C., with toluene the temperature will be in the order of 110 C., and with xylene in the order of 140-145 C. Other preferred solvents include cumene, naphtha, Decalin, etc. Any suitable amount of the solvent may be employed but preferably should not comprise a large excess because this will tend to lower the reaction temperature and slow the reaction. Water formed during the reaction may be removed in any suitable manner including, for example, by operating under reduced pressure, by removing an azeotrope of water-solvent, by distilling the condensation product at an elevated temperature, etc. As hereinbeforeset forth, a higher temperature and solvent preferably are utilized in effecting the reaction in order to remove the water as it is being formed.

It is understood that the different esters which may be prepared and used in accordance with the present invention are not necessarily equivalent.

PARTIAL PHOSPHATE SALT OF THE CONDENSATION PRODUCT Another embodiment of the invention comprises an HCl salt of a partial phosphate salt of the condensation product of epihalohydrin compound and amine compound. As hereinbefore set forth, the condensation product contains a number of recurring units, each unit containing a nitrogen atom. In this embodiment of the in-- vention only a portion of the nitrogen atoms are neutralized with the phosphate, and all or a portion of the remaining nitrogen atoms are neutralized with HCl. Accordingly, this embodiment of the invention comprises: the mixed HCl-phosphate salts of the condensation product.

In forming the phosphate salt, an alkyl acid phosphate preferably is utilized and may comprise the alkyl acid orthophosphate and/ or the alkyl acid pyrophosphate. In the alkyl acid orthophosphates, the monoalkyl ester, dialkyl ester or a mixture thereof may be employed. In the alkyl acid pyrophosphates, the monoalkyl ester, dialkyl ester, trialkyl ester or mixtures thereof may be employed, the dialkyl ester being preferred and the alkoxy groups may be attached to the same or different phosphorus atoms. Generally, however, this compound will be symmetrical and, thus, the alkoxy groups will be attached to different phosphorus atoms.

Preferably at least one of the alkyl groups constituting the ester contains at least 5 and still more preferably at least 8 carbon atoms. Illustrative alkyl acid orthophosphates are set forth below, although it is understood that these are presented as preferred examples and that other suitable alkyl acid phosphates may be employed. The preferred alkyl acid orthophosphates include monoamyl acid orthophosphate, diamyl acid orthophosphate, mixture of monoand diamyl acid orthophosphates, mono hexyl acid orthophosphate, dihexyl acid orthophosphate, mixture of monoand dihexyl acid orthophosphates, monoheptyl acid orthophosphate, diheptyl acid orthophosphate, mixture of monoand diheptyl acid orthophosphates, monooctyl acid orthophosphate, dioctyl acid orthophosphate, mixture of monoand dioctyl acid orthophosphates, monononyl acid orthophosphate, dinonyl acid orthophosphate, mixture of monoand dinonyl acid orthophosphates, monodecyl acid orthophosphate, didecyl acid orthophosphate, mixture of monoand didecyl acid orthophosphates, monoundecyl acid orthophosphate, diundecyl acid orthophosphate, mixture of monoand diundecyl acid orthophosphates, monododecyl acid orthophosphate, didodecyl acid orthophosphate, mixture of monoand didodecyl acid orthophosphates, monotridecyl acid orthophosphate, ditridecyl acid orthophosphate, mixture of monoand ditridecyl acid orthophosphates, monotetradecyl acid orthophosphate, ditetradecyl acid orthophosphate, mixture of monoand ditetradecyl acid ortho phosphates, monopentadecyl acid orthophosphate, dipentadeeyl acid orthophosphate, mixture of monoand dipentaafieeyl acid orthophosphates, etc.

Preferred alkyl acid pyrophosphates include monooctyl acid pyrophosphate, dioctyl acid pyrophosphate, mixture of monoand dioctyl acid pyrophosphates, monononyl acid pyrophosphate, dinonyl acid pyrophosphate, mixture of monoand dinonyl acid pyrophosphates, monodecyl :acid pyrophosphates, didecyl acid pyrophosphate, mixture of monoand didecyl acid pyrophosphates, monoundecyl acid pyrophosphate, diundecyl acid pyrophosphate, mixture of monoand diundecyl acid pyrophosphates, monododecyl acid pyrophosphate, didodecyl acid pyrophosphate, mixture of monoand didodecyl acid pyrophosphates, monotridecyl acid pyrophosphate, ditridecyl acid pyrophosphate, mixture of monoand ditridecyl acid pyrophosphates, monotetradecyl acid pyrophosphate, ditetradecyl acid pyrophosphate, mixture of monoand ditetradecyl acid pyrophosphates, monopentadecyl acid pyrophosphate, dipentadecyl acid pyrophosphate, mixture of monoand dipentadecyl acid pyrophosphates, etc.

Conveniently, alkyl groups containing more than 8 carbon atoms are introduced through the use of fatty alcohols and thus the alkyl radical may be selected from capryl, lauryl, myristyl, palmityl, stearyl, ceryl, etc. Illustrative phosphates in this class include stearyl capryl acid orthophosphate, distearyl acid orthophosphate, dicapryl acid orthophosphate, etc. In other examples, one of the alkyl groups contains less than 8 carbon atoms while the second alkyl group contains more than 8 carbon atoms, and such examples are illustrated by ethyl lauryl acid orthophosphate, ethyl stearyl acid orthophosphate, hexyl lauryl acid orthophosphate, hexyl capryl acid orthophosphate, 'hexyl stearyl acid orthophosphate, etc.

Alkyl acid phosphates including both the ortho and pyrophosphates also are manufactured commercially as a mixture of monoand dialkyl acid phosphates and are available at lower costs. In many cases, such mixtures are suitable for use in preparing the salt and such use, therefore, is preferred for economic reasons.

As hereinbefore set forth, the partial phosphate salt of the condensation product of epihalohydrin-amine is prepared. Accordingly, the alkyl acid phosphate will be used in a proportion of at least one mol of alkyl acid phosphate per mol of condensation product and will range up to one mol of phosphate per each mol equivalent less one of basic nitrogen in the ester. In general this will comprise from about 2 to about 19 mols of phosphate per 1 mol of condensation product. For example, as hereinbefore set forth, the preferred condensation product formed by the reaction of one mol of epichlorohydrin per one mol of amine compound will contain from about 3 to about 20 and preferably from about 5 to about 10 recurring units, each unit containing a basic nitrogen. Accordingly, from about 2 to about 19 mols of phosphate are used per mol of condensation product in order to obtain the desired partial phosphate. It is understood that, when a condensation product contains more than 20 basic nitrogens, a correspondingly larger amount of phosphate may be used.

The partial phosphate of the condensation product may be prepared in any suitable manner and either before but preferably after the HCl salt is prepared. The phosphate salt is readily prepared by mixing the alkyl acid orthophosphate and the condensation product, preferably the HCl salt of the condensation product, at ambient temperature, with vigorous stirring, although slightly elevated temperatures which generally will not exceed 200 F. may be employed, when desired. Excessive temperatures must not be used in order to avoid decomposition reactions. In fact, the reaction is slightly exothermic and in some cases it may be desirable to cool the reaction vessel. The reaction may be effected in the presence or absence of a solvent. When employed, the solvent may be used either in forming a more fluid mixture of the reactants before mixing and/ or during the mixing thereof. Any suitable solvent may be employed and preferably is an aromatic hydrocarbon including benzene, toluene, xylene, ethylbendene, cumene, etc., or mixtures thereof. In other cases the solvent may be selected from alcohols, ethers, ketones, etc. In many cases it is desired to market the final product as a solution in a suitable solvent and conveniently the same solvent is used during the preparation of the phosphate and/ or HCl salts.

PARTIAL PHOSPHATE SALT OF THE ESTER OF THE CONDENSATION PRODUCT In still another embodiment, the additive of the present invention comprises an HCl salt of the partial phosphatesalt of the ester of the condensation product. Accordingly, the additive comprises the mixed HCl-phosphate salt of the ester. The phosphate salt of the ester is prepared in substantially the same manner as heretofore described in detail for the preparation of the partial phosphate salt of the condensation product. Instead of the condensation product, an ester thereof prepared in the manner as hereinbefore set forth in the description of the preparation of the ester, is reacted with the alkyl acid phosphate. Here again, preferably the HCl salt is formed first and then the phosphate salt of the ester is prepared. Because the preparation of the ester and the preparation of the partial phosphate salt have been described in detail hereinbefore, it is unnecessary to repeat the details to describe the preparation of the partial phosphate salt of the ester. A specific preparation will be described in the appended examples.

HC'l SALT As hereinbefore set forth, the novel additive of the present invention comprises an HCl salt of the condensation product of an epihalohydrin compound with an amine, a carboxylic acid ester thereof or partial phosphate salt of the condensation product or ester. Preferably only a portion of the amino nitrogen in said condensation product or ester are neutralized. Of necessity, only a portion of the amino nitrogens of the partial phosphate salt will be neutralized. It is recognized that the =HCl salt will be less soluble in hydrocarbon oil than the condensation product, ester or partial phosphate salt and, therefore, it is important that the extent of neutralization with HCl be below that exceeding solubility of the hydrocarbon oil. At least 0.2% of the amino nitrogens will be neutralized with HCl, and the upper limit of neutralization with HCl will be that at which solubility of the additive in the hydrocarbon oil is exceeded. The solubility is determined by the concentration of additive to be incorporated in the oil. In general it is preferred that from about 1% to about 20% of the amino nitrogen is neutralized with HCl.

Neutralization with HCl is effected in any suitable manner and in general is readily accomplished by heating, with stirring, a mixture of the condensation product, ester or partial phosphate salt and HO]. \The HCl may be utilized as a gas in a closed system. However, it preferably is utilized as a solution in a suitable solvent including alcohol, water, etc. The lower alcohols are preferred solvents and include methanol, ethanol, propanol, and butanol. In general the reaction is effected at ambient or elevated temperature, which may range from about 50 to about C. and, as stated before, with stirring. Higher temperatures may be used in some cases, but generally offer no advantages. When a solvent is employed, it may be removed by distillation under vacuum or in any other suitable manner, although in some cases it may be desirable to market the additive as a solution in the solvent. When water is used as the solvent, the water preferably is removed by azeotropic distillation.

The HCl salt recovered in the above manner may be utilized as such or prepared as a solution in a suitable solvent. Aromatic hydrocarbons are particularly preferred solvents and include benzene, toluene, xylene, ethylbenzene, cumene, etc. It is understood that other suitable organic compounds and particularly parafiinic hydrocarbons may be used as solvents.

The additive prepared in the above manner is incorporated :in a hydrocarbon oil in an amount of from about 1 to about 1000 parts per million by weight of the hydrocarbon oil and preferably in a concentration of from about 5 to about 100 parts per million, although higher concentrations up to 1% by Weight may be used in some cases and thus may range from about 0.0005 to about 1% by weight.

As hereinbefore set forth, the salt of the present invention is used to prevent deposit formation :in heat exchangers. In such heat exchange one fluid is passed through tubes or coils disposed in a shell and the other fluid is passed through the shell. The oil heated in this manner then is passed for further treatment, while the oil cooled in this manner is passed to separation or further conversion. It is understood that the hydrocarbon oil may comprise gasoline, naphtha, kerosene, gas oil, burner oil, diesel oil, fuel oil, residual oil, etc.

An example of a process in which the charge is passed in heat exchange with hot effluent products is a hydrotreating process in which oil is subjected to hydrogen treating in the presence of a catalyst comprising aluminamolybdenum oxide-cobalt oxide or alumina-molybdenum sulfide-cobalt sulfide. The oil may comprise gasoline, kerosene, gas oil or mixtures thereof and is treated to remove impurities including sulfur compounds, nitrogen compounds, oxygen compounds, metals, etc. The treating is effected at a temperature within the range of from about 500 to about 800 F. or more at hydrogen pressures of from about 100 to about 1000 pounds per square inch or more. The oil charged to the process generally is introduced at a temperature of from ambient to 200 F. and is passed in heat exchange with products withdrawn from the reactor at a temperature of from about 500 to about 800 F. During this heat exchange the charge is heated to a temperature of from about 300 to about 600 F. and then may be heated further in a furnace or otherwise to the temperature desired for effecting the treating. -At the same time the hot reactor effluent products are cooled to a temperature of from about 300 to about 600 F. and below that at which they are withdrawn from the reactor. General-1y the partly cooled reactor efliuent products are cooled further by heat exchange with water or otherwise and then are passed into a separator, wherefrom gases and liquids are each separately withdrawn. Another illustrative example of a process in which the charge is passed in heat exchange with reactor effluent products is a reforming process in which gasoline is contacted with hydrogen in the presence of a platinum-containing catalyst at .a temperature of from about 700 to about 1000 F.

An example in which oil is subjected to fractionation and the charge is passed in heat exchange with the hot effluent products is in a crude column. In this column, crude oil is subjected to distillation at a temperature of from about 600 to about 700 F. in order to remove lighter components as overhead and/or side streams. In some cases the charge first is passed in heat exchange with the overhead and/or side streams from this column and then is passed in heat exchange with the hotter products withdrawn from the bottom of the crude column. In this way the charge is progressively heated and the hotter products are cooled.

Normally the charge to the treating or conversion process contains components which form deposits in the heat exchangers and, accordingly, the salt of the present invention is incorporated in the charge prior to entering the heat exchanger. In most cases the charge after heat exchange is subjected to fractionation to separate a particular stream for subjecting to further treating or conversion in the presence of a catalyst. Generally this stream comprises the light or intermediate components of the charge, and the heavier components of the charge are removed from the process. In most cases the salt will be retained in the bottoms product and therefore will not contact the catalyst used in the subsequent treating or conversion steps. However, the salt in the small conoentrations used will not adversely affect most catalysts, and therefore would be of concern only with processes using catalysts of extreme sensitivity. As stated above, even with such catalysts, the prefractionation will serve to retain the salt in the heavier products and the salt therefore will not contact the catalyst.

Another example in which hydrocarbon oil is passed in heat exchange is in the case of jet fuel, wherein the jet-fuel is passed in heat exchange with hot lubricating oil. Temperatures as high as 500 F. or more are encountered .for at least short periods of time, with the result that deposit formation occurs and either interferes with eflicient heat transfer or, in extreme cases, plugs the heat exchanger.

As hereinbefore set forth, the additive of the present invention also may be used to improve the storage stability and other properties of hydrocarbon oil. These hydrocarbon oils include gasoline, naphtha, kerosene, gas oil, burner oil, diesel oil, fuel oil, lubricating oil, residual oil, etc.

While the present invention is particularly applicable to the treatment of hydrocarbon fluids, it is understood that it may be employed with other organic fluids which cause deposit formation in heat exchangers as in storage. Such other organic fluids include alcohols, aldehydes, ketones, detergents, pharmaceuticals, organic intermediates, etc.

It is understood that the salt of the present invention may be used along with other additives including, for example, antioxidant, metal deactivator, corrosion inhibitor, detergent, dye, etc. The specific additive to be used will depend upon the particular hydrocarbon oil being treated.

The following examples are introduced to illustrate further the novelty and utility of the present invention but not with the intention of unduly limiting the same.

Example I A number of different I-ICl salts of the condensation product of epichlorohydrin and tallow amine were prepared. The condensation product was prepared by the reaction of equal mol proportions of hydrogenated tallow amine (Armeen HTD) and epichlorohydrin. It will be noted that the tallow amine is a mixture of primary alkyl amines predominating in 16 to 18 carbon atoms per alkyl group. The reaction was effected by first forming a solution of 2 mols of epichlorohydrin in 600 cc. of a solvent mixture comprising 400 cc. of xylene and 200 cc. of 2-propanol. A separate solution of 2 mols of Armeen HTD was prepared inan equal volume of xylene. One mol of the latter solution was added gradually to the epichlorohydrin solution, with stirring and heating at 55 60 C. for a period of 2.5 hours. Then another mol of Armeen HTD was added gradually to the reaction mixture, stirred and reacted at 80 C. for 2.5 hours. One mol of sodium hydroxide then was added 12 with stirring and heating at 90 C. for 3.5 hours, after which another mol of sodium hydroxide was added and the mixture stirred and reacted at 85-90 C. for one hour. Following completion of the reaction, the mixture was cooled, filtered, and the filtrate then was distilled to remove the alcohol. The condensation product was recovered as a 50% by weight solution of active ingredient in xylene.

The HCl salts of the condensation product formed in the above manner were prepared by reacting a specified concentration of HCl in the form of 0.0951 N alcoholic HCl with different samples of the condensation product. All of these preparations were made by mixing the reactants as stated above at room temperature, with stirring, then heating on a water bath to a temperature of about C. for about 1 hour, following which the rest of the alcohol was removed by distillation under water pump vacuum. Additional xylene was then added to each preparation to form a final solution of 50% by weight active ingredient.

The specific details of preparation and certain analytical data are reported in the following table:

TABLE I Gms. of Percent of conden- Co. of amino Additive Number sation alcoholic nitrogen product H01 neutralized with H01 As hereinbefore set forth, the above salts were recovered as solutions in xylene of 50% by weight active ingredient. All of these solutions are amber, free-flowing liquids. Additive 2 had an index of refraction (n of 1.4833. Additive 3 had an index of refraction (n of 1.4823. Additive 4 had an index of refraction (n of 1.4802. Addiitive 5 had an index of refraction (11 of 1.4761.

Example 11 As hereinbefore set forth, the HCl salts of the present invention are particularly desirable for use to prevent heat exchanger deposits. The different additives prepared as described in Example I were evaluated in the C.F.R. Fuel Coker Thermal Stability Test. In this test, the oil heated to the specified temperature is passed through the annular space surrounding a heated inside tube of 17" length and /2" diameter positioned with an outside tube of inside diameter. The inside tube is heated by means of a heating coil positioned therein to a temperature of either 300 or 400 F. depending upon the particular fuel being evaluated. The test is conducted for :300 minutes, at a pressure of 160 pounds per square inch, and a flow rate of 6 pounds of fuel per hour. Following the run the equipment is dismantled, 13" or less of the inner tube is marked off in 1" increments, and the deposits on the heated inner tube are rated by visual comparison with standard metal coupons. In general the rating is substantially as follows:

0clean and bright,

1meta1 dulled but not discolored, 2-light yellow discoloration, 3yellow to tan discoloration, 4anything darker or heavier than 3.

The ratings of the individual 1" increments are added together to give a final tube rating. Military specifications for jet fuels require that none of the 1" increments rate poorer than 3.

' The fuel used in these evaluations is a commercial heavy catalytic naphtha and was tested at .a temperature of 400 F. A control sample (not containing an additive) 13 of the naphtha gave a tube rating of '26 when evaluated in the above manner. The results of evaluating the different samples of the naphtha containing the additives described in Example I are reported in the following From the data in the above table it will be noted that the additives of the present invention all served to reduce the tube rating to about one-half of that obtained in the absence of the additive. As hereinbefore set forth, this serves to reduce deposit formation in heat exchangers.

Example III The additive of this example is an HCl salt of an ester of the condensation product prepared in the manner described in Example I. The ester is the VR1 acid ester. As hereinbefore set forth, VR1 acid is a mixture of polybasic acids, predominantly dibasic, containing about 37 carbon atoms per molecule. The ester was prepared by mixing 63.8 grams of the condensation product prepared as described above, 34.3 grams of JR- 1 acid and 100 cc. of xylene. The mixture was heated, with stirring, to a temperature of about 141 C. and refluxed for about 9 hours. The mixture was cooled and distilled under vacuum at about 155 C. to remove the xylene. The product was recovered as a viscous dark liquid and was blended with additional xylene to prepare a solution of 50% by weight active ingredient.

grams of the ester solution prepared in the above manner were mixed with 1.6 cc. of 0.0951 N alcoholic HCl and heated, with stirring, to a temperature of about 98 C. for about 1 hour, after which the rest of the alcohol was removed by distilling under water pump vacuum. Sufficient xylene was added to form a final solution of 50% by weight active ingredient. This product was a dark brown, opaque, free-flowing liquid, having an index of refraction (n of 1.4867.

The salt prepared in the above manner was evaluated according to the C.F.R. Fuel Coker Thermal Stability Test described in Example II. The control sample (not containing an additive) of the oil used in this example had a tube rating of 20. Another sample of the oil containing 0.005% by weight of active ingredient of the salt prepared as described above, when evaluated in this manner, had a tube rating of 12. Here again it will be noted that the additive of the present invention was effective in reducing deposit formation.

Example IV As hereinbefore set forth, another embodiment of the invention comprises mixed HCl-phosphate salts of the condensation product of epihalohydrin with amine. The phosphate salt is the mixed mon-oand ditridecyl acid orthophosphate salt of the condensation product prepared as described in Example I. In this preparation the HCl salt was prepared first and then the phosphate salt was prepared.

100 grams of the 50% active ingredient solution of the condensation product prepared in the manner described in Example I and 156 cc. of 0.0951 N HCl solution in isopropanol were commingled at room temperature and reacted with stirring for 15 minutes. 49.3 grams of mixed monoand ditridecyl acid orthophosphate were commingled therewith and the mixture heated, with stirring, to 50 C. for 45 minutes. The mixture then was distilled under water pump vacuum to remove the rest of the alcohol. Sufiicient xylene then was commingled with the product to produce a 50% solution active ingredient. This solution was recovered as an amber, free-flowing liquid, having an index of refraction (n of 1.4787.

The mixed HCl-phosphate salt prepared in the above manner was evaluated according to the C.F.R. Fuel Coker Thermal Stability Test described in Example 11. The oil used in this example is a commercial JP-4 jet fuel and the test was conducted at a temperature of 300 F. A control sample (not containing an additive) of the jet fuel, when evaluated in the above manner, had a tube rating of 34. In contrast, another sample of the jet fuel containing 0.0025 by weight of the mixed HCl-phosphate salt solution (0.00125 by weight of active ingredient) described above, when evaluated in the above manner, had a tube rating of zero. It is apparent that the additive of the present invention was very effective in reducing deposit formation.

Example V As hereinbefore set forth, the additive of the present invention also is effective to prevent sediment formation in hydrocarbon oil. The sediment formation will cause plugging of filters, strainers, burner tips, injectors, etc., and the efficacy of the additive is evaluated in a method referred to as the Erdco Test. In this method, heated oil is passed through a filter, and the time required to develop a differential pressure across the filter of 25 incHg is determined. It is apparent that the longer the time, the more effective is the additive. However, with a very effective additive, the time to reach a differential pressure across the filter of 25 in. Hg is lengthened beyond reasonable limits and the test is stopped after about 300 minutes and the differential pressure at that time is reported. The oil used in this example is the JP-4 jet fuel described in Example IV. In this test the preheater was run at 300 F. and the filter at 400 F.

When evaluated in the above manner a control sample (not contianing an additive) of the jet fuel developed a differential pressure across the filter of 25 in. Hg in 130 minutes. On the other hand, another sample of this jet fuel containing 0.0025% by weight of the mixed HClphosphate salt solution (0.00l25% by weight active ingredient) described in Example IV, developed a differential pressure of only 0.5 in. Hg after 300 minutes.

Example VI The mixed HCl-phosphate salt prepared as described in Example 1V also was evaluated in the Erdco Test in a commercial JP-6 fuel. This test was conducted using a preheater temperature of 400 F. and a filter temperature of 500 F.

A control sample (not containing an additive) of the JP-6 jet fuel, when evaluated in the Erdco Test as described above, developed a differential pressure of 25 in. Hg in 51 minutes. On the other hand, another sample of the jet fuel containing 0.0025 by weight of the 50% solution (0.00125% active ingredient) of the mixed HClphosphate salt prepared as described in Example W, developed a zero in. Hg pressure after 300 minutes.

At the same time, the preheater tube rating of the mixed HCl-phosphate salt described above was evaluated. A control sample (not containing an additive) of the JP-6 fuel had a tube rating of 15. The sample of the ZIP-6 fuel containing the mixed HCl-phosphate salt described above had a tube rating of only 6. From the above data it will be seen that the additive was very effective in preventing filter plugging and tube deposits.

Example VII The additive of this example is the mixed HCl-phosphate salt of an ester of the condensation product of epichlorohydrin and tallow amine. The condensation product was prepared substantially in the same manner as described in Example I. The ester was prepared by refluxing grams of the 50% active solution of the condensation product, 42 grams of oleic acid and 50 cc. of

xylene. The refluxing was elTected at about 150 C. for 15 hours. An 0.1 N solution of HCl-ethanol is mixed with the ester prepared in the above manner and the mixture is heated, with stirring, at 85 C. for 1 hour. The HCl is used in a concentration to neutralize 10% of the basic amino nitrogen. Mixed monoand diisooctyl acid orthophosphate is added to the mixture and heated, with stirring, at 50 C. for 40 minutes. Suflicient xylene then is added to produce a final solution of 50% by Weight active ingredient.

The mixed HCl-phosphate salt of the ester prepared in the above manner is incorporated in a straight run oil having a boiling range of from about 300 to about 700 F., which oil is passed in heat exchange with hot reactor efiluent products. The thus preheated charge then is heated in a furnace to a temperature of 600 F. and passed in contact with alumina-molybdenum oxide-cobalt oxide catalyst to remove sulfur, nitrogen and other impurities from the oil. The reactor eflluent products are passed in heat exchange with the charge as described above and then are sent to a separator for the removal of hydrogen and hydrocarbon gases, after which the oil is sent to a fractionating zone to separate a naphtha having an end boiling point of 400 F. and a heavier oil having a boiling range of from about 400 to about 700 F.

I claim as my invention:

1. An oil soluble HCl salt of an ester of stoichiometric amounts of an aliphatic carboxylic acid of from about 6 to about 50 carbon atoms per molecule and the polymeric condensation product, formed at a temperature of from about C. to about 150 C., of one mol proportion of an alkyl amine selected from the group consisting of primary and secondary amines containing from about 12 to about 40 carbon atoms per molecule with one mol proportion of an epihalohydrin compound selected from the group consisting of epi-chlorohydrin, 1,2-epi-4-chlorobutane, 2,3-epi-4-chlorobutane, 1,2-epi-5- chloropentane, 2,3-epi-5-chloropentane and corresponding bromo and iodo compounds, thereafter reacting with an inorganic base selected from the group consisting of sodium hydroxide and potassium hydroxide at a temperature of from about 20 C. to about 150 C. to liberate the free amine, thereby forming an inorganic halide salt, removing said salt, and further reacting at a temperature of from about 20 C. to about 150 C. to form said polymeric condensation product, from about 1% to about 20% of the amino nitrogen in said condensation product being neutralized with HCl.

2. An oil soluble HCl salt of the polymeric condensation product, formed at a temperature of from about 20 C. to about 150 C., of one mol proportion of an aliphatic amine selected from the group consisting of primary and secondary amines containing from about 12 to about 40 carbon atoms per molecule with one mol proportion of an epihalohydrin compound selected from the group consisting of epichlorohydrin, 1,2-epi-4-chloro butane, 2,3-epi-4-chlorobutane, 1,2-epi-5-chloropentane, 2,3-epi-5 -chloropentane and corresponding bromo and iodo compounds, there after reacting with an inorganic base selected from the group consisting of sodium hydroxide and potassium hydroxide at a temperature of from about 20 C. to about C. to liberate the free amine, thereby forming an inorgainc halide salt, removing said salt, and further reacting at a temperature of from about 20 C. to about 150 C. to form said polymeric condensation product, from about 1% to about 20% of the amino nitrogen in said condensation product being neutralized with HCl.

- 3. An oilso'luble mixed HCl-alkyl acid phosphate salt of the polymeric condensation product, formed at a temperature of from about 20 C. to about 150 C., of one mol proportion of an alkyl amine selected from the .group consisting of primary and secondary amines containing from about 12 to about 40 carbon atoms per molecule with one mol proportion of an epihalohydrin compound selected from the group consisting of epichlorohydrin, 1,2-epi-4-chlorobutane, 2,3-epi-4-chlorobutane, 1,2-epi-5-chloropentane, 2,3-epi-5-chloropentane and corresponding bromo and iodo compounds, thereafter reacting with an inorganic base selected from the group consisting of sodium hydroxide and potassium hydroxide at a temperature of from about 20 C. to about 150 C. to liberate the free amine, thereby forming an inorganic halide salt, removing said salt, and further reacting at a temperature of from about 20 C. to about 150 C. to form said polymeric condensation product, from about 1% to about 20% of the amino nitrogen in said condensation product being neutralized with HCl and the amount of alkyl acid phosphate being at least one mol of phosphate per mol of the condensation product.

4. An oil soluble HCl salt of the polymeric condensation product, formed at a temperature of from about 20 C. to about 150 C., of equimolar amounts of epichlorohydrin and an alkyl amine selected from the group consisting of primary and secondary amines having from about 12 to about 40 carbon atoms per molecule, thereafter reacting with an inorganic base selected from the group consisting of sodium hydroxide and potassium hydroxide at a temperature of from about 20 C. to about 150 C. to liberate the free amine, thereby forming an inorganic halide salt, removing said salt, and further reacting at a temperature of from about 20 C. to about 150 C. to form said polymeric condensation product, from about 1% to about 20% of the amino nitrogen in said condensation product being neutralized with HCl.

5. An oil soluble HCI salt of the polymeric condensation product, formed at a temperature of from about 20 C. to about 150 C., of equimolar amounts of epichlorohydrin and tallow amine, thereafter reacting with an inorganic base selected from the group consisting of sodium hydroxide and potassium hydroxide at a temperature of from about 20 C. to about 150 C. to liberate the free amine, thereby forming an inorganic halide salt, removing said salt, and further reacting at a temperature of from about 20 C. to about 150 C. to form said polymeric condensation product, from about 1% to about 20% of the amino nitrogen in said condensation product being neutralized with HCl.

6. An oil soluble HCl salt of an ester of carboxylic acid containing from about 6 to about 50 carbon atoms per molecule and the polymeric condensation product, formed at a temperature of from about 20 C. to about 150 C., of equimolar amounts of epichlorohydrin and an alkyl amine selected from the group consisting of primary and secondary amines of from about 12 to about 40 carbon atoms per molecule, thereafter reacting with an inorganic base selected from the group consisting of sodium hydroxide and potassium hydroxide at a temperature of from about 20 C. to about 150 C. to liberate the free amine, thereby forming an inorganic halide salt, removing said salt, further reacting at a temperature of from about 20 C. to about 150 C., to form said polymeric condensation product, from about 1% to about 20% of the amino nitrogen in said condensation product being neutralized with HCl and the amount of carboxylic acid being sufiicient to este-rify from one to all of the hydroxyl groups in the condensation product.

7. An oil soluble mixed HCl-alkyl acid phosphate salt of the polymeric condensation product, formed at a temperature of from about 20 C. to about 150 C., of equimolar amounts of epichlorohydrin and an alkyl amine selected from the group consisting of primary and secondary amines of from about 12 to about 40 carbon atoms per molecule, thereafter reacting with an inorganic base selected from the group consisting of sodium hydroxide and potassium hydroxide at a temperature of from about 20 C. to about 150 C. to liberate the free amine, thereby forming an inorganic halide salt, removing said salt, and further reacting at a temperature of from about 17 20 C. to about 150 C. to form said polymeric condensation product, from about 1% to about 20% of the amino nitrogen in said condensation product being neutralized with HCl and the amount of alkyl acid phosphate being at least one mol of phosphate per mol of the condensation product.

8. An oil soluble HCl salt of the polymeric condensation product, formed at a temperature of from about 20-150 C., of one mol proportion of epichlorohydrin with one mol proportion of tallow amine, thereafter reacting with an inorganic base selected from the group consisting of sodium hydroxide and potassium hydroxide at a temperature of from about 20 C. to about 150 C. to liberate the free amine, thereby forming an inorto form said polymeric condensation product, from about 1% to about 20% of the amino nitrogen in said condensation product being neutralized with HCl.

References Cited by the Examiner UNITED STATES PATENTS CHARLES B. PARKER, Primary Examiner.

ganic halide salt, removing said salt, and further reacting 15 ABRAHAM WINKELSTEIN, JOSEPH BRUST,

at a temperature of from about 20 C. to about 150 C.

Examiners. 

1. AN OIL SOLUBLE HCL SALT OF AN ESTER OF STOICHIOMETRIC AMOUNTS OF AN ALIPHATIC CARBOXYLIC ACID OF FROM ABOUT 6 TO ABOUT 50 CARBON ATOMS PER MOLECULE AND THE POLYMERIC CONDENSATION PRODUCT, FORMED AT A TEMPERATURE OF FROM ABOUT 20*C. TO ABOUT 150*C., OF ONE MOL PROPORTION OF AN ALKYL AMINE SELECTED FROM THE GROUP CONSISTING OF PRIMARY AND SECONDARY AMINES CONTAINING FROM ABOUT 12 TO ABOUT 40 CARBON ATOMS PER MOLECULE WITH ONE MOL PROPORTION OF AN EPIHALOHYDRIN COMPOUND SELECTED FROM THE GROUP OF EPI-CHLOROHYDRIN, 1,2-EPI-4-CHLOROBUTANE, 2,3-EPI-4-CHLOROBUTANE, 1,2-EPI-5CHLOROPENTANE, 2,3-EPI-5-CHLOROPENTANE AND CORRESPONDING BROMO AND IODO COMPOUNDS, THEREAFTER REACTING WITH AN INORGANIC BASE SELECTED FROM THE GROUP CONSISTING OF SODIUM HYDROXIDE AND POTASSIUM HYDROXIDE AT A TEMPERATURE OF FROM ABOUT 20*C. TO ABOUT 150*C. TO LIBERATE THE FREE AMINE, THEREBY FORMING AN INORGANIC HALIDE SALT, REMOVING SAID SALT, AND FURTHER REACTING AT A TEMPERATURE OF FROM ABOUT 20*C. TO ABOUT 150*C. TO FORM SAID POLYMERIC CONDENSATION PRODUCT, FROM ABOUT 1% TO ABOUT 20% OF THE AMINO NITROGEN IN SAID CONDENSATION PRODUCT BEING NEUTRALIZED WITH HC1. 